Efficient Homolytic Cleavage of H 2 O 2 on Hydroxyl‐Enriched Spinel CuFe 2 O 4 with Dual Lewis Acid Sites

Abstract Traditional H 2 O 2 cleavage mediated by macroscopic electron transfer (MET) not only has low utilization of H 2 O 2 , but also sacrifices the stability of catalysts. We present a non‐redox hydroxyl‐enriched spinel (CuFe 2 O 4 ) catalyst with dual Lewis acid sites to realize the homolytic cleavage of H 2 O 2 . The results of systematic experiments, in situ characterizations, and theoretical calculations confirm that tetrahedral Cu sites with optimal Lewis acidity and strong electron delocalization can synergistically elongate the O−O bonds (1.47 Å → 1.87 Å) in collaboration with adjacent bridging hydroxyl (another Lewis acid site). As a result, the free energy of H 2 O 2 homolytic cleavage is decreased (1.28 eV → 0.98 eV). H 2 O 2 can be efficiently split into ⋅OH induced by hydroxyl‐enriched CuFe 2 O 4 without MET, which greatly improves the catalyst stability and the H 2 O 2 utilization (65.2 %, nearly 2 times than traditional catalysts). The system assembled with hydroxyl‐enriched CuFe 2 O 4 and H 2 O 2 affords exceptional performance for organic pollutant elimination. The scale‐up experiment using a continuous flow reactor realizes long‐term stability (up to 600 mL), confirming the tremendous potential of hydroxyl‐enriched CuFe 2 O 4 for practical applications.